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Supercapacitors ____________________________________________________

Study of Supercapacitors (Construction of Supercapacitors)

Piyush Tulsidas Itankar1
AbstractSupercapacitors are advanced version of conventional capacitors. These can have capacities ranging from a Farad to thousands of Farads. The revolution in Chemical Engineering has enabled these capacitors to come out as perfect combination of Power and Energy storage. Thus making them capable of replacing the conventional batteries. This paper deals with the over all construction, working, scope and advantages of Supercapacitors. Apart from this an attempt to compare Supercapacitors with conventional Capacitors and spot the major difference has been made.
Index Terms Supercapacitor, Electric Double Layer Capacitor, Ultra-capacitor, Hybrid Power Storage, Capa-Bus, Electric Vehicles

I.

INTRODUCTION

The Supercapacitors, also known as Ultracapacitor or double-layer capacitor, differs from a regular capacitor in that it has a very high capacitance. A capacitor stores energy by means of a static charge as opposed to an electrochemical reaction. Applying a voltage differential on the positive and negative plates charges the capacitor. This is similar to the buildup of electrical charge when walking on a carpet. Touching an object releases the energy through the finger. We group capacitors into three family types and the most basic is the electrostatic capacitor, with a dry separator. This capacitor has a very low capacitance and is used to filter signals and tune radio frequencies. The size ranges from a few pico-farad (pf) to low microfarad (uF). The next member is the electrolytic capacitor, which is used for power filtering, buffering and coupling. Rated in microfarads (uF), this capacitor has several thousand times the storage capacity of the electrostatic capacitor and uses a moist separator. The third type is the supercapacitor, rated in farads, which is again thousands of times higher than the electrolytic capacitor. The supercapacitor is ideal for energy storage that undergoes frequent charge and discharge cycles at high current and short duration. Farad is a unit of capacitance named after the English physicist Michael Faraday. One farad stores one coulomb of electrical charge when applying one volt. One microfaradis one million times smaller than a farad, and one pico-farad is again one million times smaller than the microfarad. Engineers at General Electric first experimented with the electric double-layer capacitor, which led to the development of an early type of supercapacitor in 1957. There were no known commercial applications then. In 1966, Standard Oil rediscovered the effect of the double-layer capacitor by accident while working on experimental fuel cell designs. The
Corresponding author: Piyush Itankar (pitankar@gmail.com).

company did not commercialize the invention but licensed it to NEC, which in 1978 marketed the technology as supercapacitor for computer memory backup. It was not until the 1990s that advances in materials and manufacturing methods led to improved performance and lower cost. The modern supercapacitor is not a battery per se but crosses the boundary into battery technology by using special electrodes and electrolyte. Several types of electrodes have been tried and we focuse on the double-layer capacitor (DLC) concept. It is carbon-based, has an organic electrolyte that is easy to manufacture and is the most common system in use today. [1]

II. HISTORY OF CAPACITORS

In October 1745, Ewald Georg von Kleist of Pomerania in Germany found that charge could be stored by connecting a highvoltage electrostatic generator by a wire to a volume of water in a handheld glass jar. Von Kleist's hand and the water acted as conductors, and the jar as a dielectric (although details of the mechanism were incorrectly identified at the time). Von Kleist found, after removing the generator, that touching the wire resulted in a painful spark. In a letter describing the experiment, he said "I would not take a second Figure 1 Primitive Capacitor

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shock for the kingdom of France." The following year, the Dutch physicist Pieter van Musschenbroek invented a similar capacitor, which was named the Leyden jar, after the University of Leiden where he worked. Daniel Gralath was the first to combine several jars in parallel into a "battery" to increase the charge storage capacity. Benjamin Franklin investigated the Leyden jar and "proved" that the charge was stored on the glass, not in the water as others had assumed. He also adopted the term "battery", (denoting the increasing of power with a row of similar units as in a battery of cannon), subsequently applied to clusters of electrochemical cells. Leyden jars were later made by coating the inside and outside of jars with metal foil, leaving a space at the mouth to prevent arcing between the foils. The earliest unit of capacitance was the 'jar', equivalent to about 1 nanofarad. Leyden jars or more powerful devices employing flat glass plates alternating with foil conductors were used exclusively up until about 1900, when the invention of wireless (radio) created a demand for standard capacitors, and the steady move to higher frequencies required capacitors with lower inductance. A more compact construction began to be used of a flexible dielectric sheet such as oiled paper sandwiched between sheets of metal foil, rolled or folded into a small package. Early capacitors were also known as condensers, a term that is still occasionally used today. The term was first used for this purpose by Alessandro Volta in 1782, with reference to the device's ability to store a higher density of electric charge than a normal isolated conductor.[2] one plate and exactly opposite type is accumulated on the other plate, naturally. The accumulation of charge occurs under the presence of external electric potential on the plates which is applied externally. The unit of capacitance is Farad after the name of Michael Faraday. One Farad is the capacity due to accumulation of one coulomb charge on the plates as a result of applied unit volt of electric potential. Until the invention of Supercapacitors, Farad was considered to be extremely large unit and so milli, micro and picofarad were generally used. Considering air as the dielectric medium, the distance between the plates as 1mm the size of plates required to make a Farad can be calculated as follows : (1) Where, C is the capacitance in Farad. is the permittivity of free space. A is the Area of the plate. d is the distance between the plates. On solving area for the plate turns out to be around 2 113Km . It is impossible to make parallel plates of this size and keep them separated with 1mm distance. Thus, the limit of conventional capacitors is limited to few millifarads.

IV. SUPERCAPACITOR DESIGN

The first development step for a supercapacitor manufacturer is to make his choice between the different technologies and the different design types available: aqueous, organic, stack, winding, for example. The choice is mainly driven by the performances, the manufacturability and the costs. In this paragraph a survey of the main functions required from the different component parts has been described. A focus on the particular case of the commercial technology based on activated carbon and organic electrolyte has been treated. From a conceptual point of view, the supercapacitor cell may be considered as an assembly of three main parts: - the active part consisting of the electrodes and the separator - the electrolyte impregnant - the packaging. The supercapacitor active part is made in most of the case of two identical electrodes. There is a spacer between the electrodes, the separator, which function is to provide an electronic insulation between the electrodes, while leaving the ions moving through its porosity to insure the ionic conduction. The active part is impregnated with an electrolyte made of a solvent containing a disassociated salt and is closed in a tight package.[3]

III. LIMIT OF CAPACITORS

Considering a conventional two plate capacitor. The capacitance depends only on the physical parameter, namely distance between the plates, the plate size and the dielectric between the plates.

Figure 2 Parallel plate capacitor Conventional Capacitors are based on separating electric charge. The accumulation of one type of charge occurs on

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Figure 3 The difference in the electrodes of capacitor and super capacitor [4] ionic resistance in the electrolyte may be understood as the friction of the ions in the solvent. The ionic resistance increases with the vicosity. In static, when there is no more current, the potential would be flat in the electrolyte. The separator is a porous membrane which contains about 50% of electrolyte. The membrane provides the electronic insulation between the electrodes. A high porosity, a small percolation length and a small thickness provides a good ionic conductivity.. The different theories presented below assume different types of charge distribution at the

A. Double Layer

interface.[5]

B. Activated Carbon
Figure 4 Variation of potential At the interface between a metal and an electrolyte (liquid or gel containing ionic conductors, for example solvent with a salt) appears a charged layer. In the electrolyte the charge is made of ions; in the conductor it may be either electrons or holes. To maintain the electrical neutrality of the system, a second layer charged with the opposite charges is necessary. In the core of the electrolyte the potential drop is due to the ionic current in the resistance of the viscous solvent. The Graphite basal plane: Hexagonal structure Distance between the carbon atoms: 110 pm Graphite interlaminar distance d002 = 350 to 400 pm Carbon atomic radius: 70 pm Carbon covalent radius: 77 pm Carbon Van der Waals radius: 170 pm Surface charge estimation Carbon atomic mass: 12 g/mol 3 3 Carbon density: = 2.2 g/cm => 0.18 mol/cm

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23 23
Avogadro constant: NA = 6 10 3 atoms/cm atoms/mol = > 1.1 10

=> Carbon interatomic distance of 0.2 nm (actually d 002 = 0.35 to 0.4 nm; the discrepancy is due to the hexagonal packing in the basal plane (0.11 nm between the carbon atoms) 15 => Number of carbon atoms on a unit surface 2.3 10 2 atoms/cm Same estimation with the ions 14 2 BF4 : 0.46 nm => 5 10 molecules/cm + 14 2 -6 Et4N : 0.7 nm => 2 10 molecules/cm or 3.3 10 2 moles/m 19 -5 With a charge 1+= 1.6 10 C/charge => 3.2 10 2 Coulomb/cm

Figure 5 Carbon atom arrangement

C. Carbon Surface Charge Estimation

Carbon atomic mass: 12 g/mol 3 3 Carbon density: = 2.2 g/cm => 0.18 mol/cm 23 23 Avogadro constant: NA = 6 10 atoms/mol = > 1.1 10 3 atoms/cm => Carbon interatomic distance of 0.2 nm (actually d 002 = 0.35 to 0.4 nm; the discrepancy is due to the hexagonal packing in the basal plane (0.11 nm between the carbon atoms) 15 => Number of carbon atoms on a unit surface 2.3 10 2 atoms/cm Same estimation with the ions 14 2 BF4 : 0.46 nm => 5 x 10 molecules/cm + 14 2 -6 Et4N : 0.7 nm => 2 x 10 molecules/cm or 3.3 10 2 moles/m 19 -5 With a charge 1+= 1.6 x 10 C/charge => 3.2 10 2 Coulomb/cm

D. Capacity Density Estimation

Figure 6 The increased surface area Assuming a potential drop of 1 V on the interface layer, with Q = C U. The maximum expected capacitance 2 could be C = 32 mF/cm [6]

V. ELECTRICAL EQUIVALENT MODEL

The double-layer capacitor is a physical component which hasn't only a requested capacitance, but also an unavoidable parasitic inductance due to its geometry, a series resistance due to the electronic and ionic conductor ohmic resistances and a parallel resistance due to the leakage current between the electrodes. [7] The equivalent series resistance ESR, which is a combination of the series resistance Rs and the parallel resistance Rp (see fig. 8), is responsible for the electrical losses which generate the internal heating.

Figure 7 Perforated structure of activated carbon

Figure 8 Basic ultracapacitor electrical equivalent circuit.

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To get high power, it is absolutely necessary to have a low ESR. The parallel resistance Rp has an effect visible only at very low frequency (below the milihertz range). It is responsible for the capacitor self discharge time. Its value must be as high as possible to limit the leakage current. The time constant of the self discharge is equal to = Rp C. The transmission-line basic model used to describe the frequency behavior of the capacitance and the series resistance has been originally proposed by de Levie. This theory doesn't take into account the voltage and temperature dependences of the capacitance and series resistance. A simple model which considers an additional linear dependence of the capacitance on the tension has been proposed by Zubieta et al. Similar models have been used also by Dougal et al. and Belhachemi et al. The capacitance is composed by a constant part Co and a linear voltage dependent one where Kv is a coefficient which depends on the technology. The total capacitance at the voltage U is given by:

The stored energy is equal to the time integral of the power that leads to the relation :

The relation between the current and the voltage must be

derived from the relation between the current and the charge which remains always true. Substituting the Q expression as a function of U and C, taking into account the indirect dependence of C with the time, it is easy to show that the current is given by equation:

In conclusion, the current and the energy for a given voltage are bigger than what they were expected on the base of the classical expressions in the case of constant capacitance. [8] The capacitance and the series resistance have values which are not constant over the frequency spectrum. The performances may be determined with an Impedance Spectrum analyzer. To take into account the voltage, the temperature and the frequency dependencies, a simple equivalent electrical circuit has been developed by Rafik et al. It's a combination of the De Levie frequency model and Zubieta voltage model with the addition of a function to take into account the temperature dependence. The equivalent scheme is composed of a fixed capacitance Co connected in parallel with a variable capacitance Cv. Cv increases linearly with the voltage. The series resistance and capacitance voltage dependencies are active only in the low frequency domain which may be taken into account with the simple RvCv circuit. To get the frequency dependence, the resistance RT and the capacitance CR have been introduced in circuit 2. Their behaviour is the one of a low pass filter with a cut off frequency = RTCR. "Circuit 1" has

Figure 9 Equivalent circuit for capacitance and series resistance dependences as a function of frequency, voltage and temperature. [9] been added to take into the thermal dependence. Circuit 3 shown is required to complete the modelling regarding the leakage current and the charge redistribution. It includes two

By analogy with the classical relation, one may define a differential supercapacitor capacitance as:

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RC parallel branches with two different time constants. It also includes a parallel RF resistance which gives the long time leakage current. Basically the available capacitance is maximal at low frequency. This may be explained with the longer time available for the ions in the electrolyte to reach the surface which is located deep in the carbon pores. At higher frequency, only the superficial carbon surface is accessible for the ions. The capacitance is consequently much smaller. The series resistance is composed of an electronic and an ionic part. The electronic contribution comes from the ohmic resistance in the conductor and in the carbon particles. The ionic contribution comes from the ions mobility in the electrolyte.[10] establish a base for the testing conditions. The capacitor conditioning before the measurement is also an important parameter which may lead to great divergences in the results. The supercapacitors need hours before to reach an equilibrium state because some areas are very far or are very difficult of access for the ions. It does mean for example that after a long polarization time, the capacitance and the ESR values will be different of those found in the absence of a previous polarization. Moreover this measurement effect will be mixed with the capacitance fading due to the aging. Consequently, it is capital to always precisely define the experimental conditions of the measurements. [11]

VII. EFFECIENCY VI. PROPERTIES

From an electrical point of view the supercapacitor is a very complex system. It is built with materials developed for the use in the battery domain and it has nevertheless capacitor like properties. The aluminum collector provides only the electronic conduction contribution to the charge transport. The separator allows only the electrolyte ionic conduction between the two electrodes. In the carbon electrode both the electronic conduction inside the carbon particle and the ionic conduction in the electrolyte around the carbon particles contribute to the electrical charge transport. The supercapacitor characterization is very sensitive to the measurement method which is used. The IEC standard organization has issued the IEC62391 series of directives to The experimental measurements have been performed at the University of Belfort on BCAP2600 supercapacitor, measuring the discharge time with a 200 W constant power. The Ragone plot curves have been obtained with the equation developped in the section "Constante power discharge" which depends only on Rs and C. The following picture shows the BCAP2600 Ragone plot for different temperatures: -40C, -20C, 0C, 20C and 60C. The efficiency is calculated with the capacitance and series resistance parameters which are deduced from the discharge curve. The curves are interrupted when the voltage at the supercapacitor terminals reach 1 V. The correlation of the time to discharge to 1 V with the experimental curves good. It's straightforward that as the voltage drops during the

Figure 10 Efficiency Curve [11]

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discharge the efficiency drops too. This is of course due to the increase of the current which compensates the voltage drop in order to maintain a constant power in the load. The consequence is that the power remains constant when the losses increase with the square of the current. ETHZ, Zurich; 2001 (http://e-collection.ethbib.ethz.ch/ecolpool/diss/fulltext/eth14413.pdf). [3] Wade TL. High power carbon-based supercapacitors. PhD submitted to the School of Chemistry, University of Melbourne; 2006. (http://eprints.infodiv.unimelb.edu.au/archive/00002521/01/Hig h_Power_Carbon-Based_Supercapacitors.pdf) [4] de Levie R. Advances in Electrochemistry and Electrochemical Engineering 1967;6:329-97. [5] Zubieta L, Bonert R, Dawson F. Considerations in the design of energy storage systems using double-layer capacitors. IPEC Tokyo 2000; 1551. [6] Dougal RA, Gao L, Liu S. Ultracapacitor model with automatic order selection and capacity for dynamic system simulation. J Power Sources 2004;126:250-7. [7] Belhachemi F, Ral S, Davat B. A physical based model of power electric double-layer supercapacitors", IEEEIAS'00, 2000, Roma. [8] Hermann V, Schneuwly A, Gallay R. High power double-layer capacitor developments and applications, ISE2001, San Francisco. [9] Kurzweil P, Fischle HJ. A new monitoring method for electrochemical aggregates by impedance spectroscopy. J Power Sources 2004;127:331-40. [10] IEC 62391-1. Fixed electric double layer capacitors for use in electronic equipment - Part 1: Generic Specification, Ed. 1. 2006. [11] IEC 62391-2. Fixed electric double layer capacitors for use in electronic equipment - Part 2: Sectional specification - Electric double layer capacitors for power application, Ed. 1. 2006.

VIII. ADVANTAGES AND APPLICATIONS

Long life, with little degradation over hundreds of thousands of charge cycles. Due to the capacitor's high number of charge-discharge cycles (millions or more compared to 200 to 1000 for most commercially available rechargeable batteries) it will last for the entire lifetime of most devices, which makes the device environmentally friendly. Rechargeable batteries wear out typically over a few years, and their highly reactive chemical electrolytes present a disposal and safety hazard. Battery lifetime can be optimized by charging only under favorable conditions, at an ideal rate and, for some chemistries, as infrequently as possible. EDLCs can help in conjunction with batteries by acting as a charge conditioner, storing energy from other sources for load balancing purposes and then using any excess energy to charge the batteries at a suitable time. Low cost per cycle. Good reversibility. Very high rates of charge and discharge. Extremely low internal resistance (ESR) and consequent high cycle efficiency (95% or more) and extremely low heating levels. High output power. High specific power. According to ITS (Institute of Transportation Studies, Davis, California) test results, the specific power of electric double-layer capacitors can exceed 6 kW/kg at 95% efficiency . Improved safety, no corrosive electrolyte and low toxicity of materials. Simple charge methodsno full-charge detection is needed; no danger of overcharging. [11]

IX. CONCLUSION
Supercapacitor as of now completes the buffer of energy and power gap between batteries and capacitors. Being capable of with holding greater power and energy simultaneously they project a future where they can replace conventional batteries. Apart from this with proper upcoming infrastructure development they are likely to replace the hybrid storage model in electric vehicles.

REFERENCES
[1] Ktz R, Carlen M. Principles and applications of electrochemical capacitors. Electrochimica Acta 2000;45: 2483-98. [2] Richner RP. Entwicklung neuartig gebundener Kohlenstoffmaterialien fr elektrische Doppelschichtkondensatorelektroden. PhD submitted to the